3-Hydroxybenzaldehyde → Methyl 3-Coumarate

HRID 1250103Notes

Reaction equation

HRID 1250103 reaction equation
[CH3:1][O:2][C:3]([CH2:5]P(OC)(OC)=O)=[O:4].[Cl-].[Li+].N12CCCN=C1CCCCC2.[OH:25][C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][CH:33]=1)[CH:29]=O>C(#N)C.O>[CH3:1][O:2][C:3](=[O:4])/[CH:5]=[CH:29]/[C:28]1[CH:31]=[CH:32][CH:33]=[C:26]([OH:25])[CH:27]=1

Participants

7

Reactant 4

HCID 1013-HydroxybenzaldehydeHCID 80029Trimethyl phosphonoacetateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 433294Lithium Chloride

Product 1

HCID 5352910Methyl 3-CoumarateYield 86.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

A solution of trimethyl phosphonoacetate (9.94 mL, 61.4 mmol), lithium chloride (2.60 g, 12.2 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (15.92 mL, 106.5 mmol) in acetonitrile (80 mL) at room temperature under a nitrogen atmosphere was stirred at room temperature for 30 minutes. 3-Hydroxybenzaldehyde (5.00 g, 40.9 mmol) was added, and the mixture was stirred at room temperature for an additional 3 hours. Water was added and the aqueous phase was extracted with diethyl ether. The combined organic fractions were washed with water, brine, dried over magnesium sulfate, and evaporated to dryness. Purification by flash chromatography, eluting with hexane/ethyl acetate, gave trans-3-(3-hydroxyphenyl)acrylic acid methyl ester as a white crystalline solid (6.30 g, 86%).

Workup

  1. extractionthe aqueous phase was extracted with diethyl ether
  2. washThe combined organic fractions were washed with water, brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated to dryness
  5. customPurification by flash chromatography
  6. washeluting with hexane/ethyl acetate

Sources & evidence

ORD record
ord-18f601cb29d44ef3a14088d63952d063
Source dataset
uspto-grants-2002_01
Patent number
US06335459B1

Reaction notes

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